Capsaicin analogues are typically synthetized by condensation of the amide group of vanillylamine with a fatty acid derivative. The enzyme of choice to perform this reaction is Candida antarctica lipase B; however, this enzyme is unable to react with the phenolic substiruents of the vanillyl ring. So far, this can only be achieved chemically, resulting in capsaicin esters with higher lipophilicity and less irritation than the parent compound. In need of searching for new capsaicin derivatives, we investigated the transesterification of the phenolic OH group of capsaicin and several capsaicin analogues by Candida antarctica lipase A (CALA) with vinyl esters. Capsaicin esters were successfully synthetized with a reaction yield of 80.6% and 57.5% with vinyl butyrate and vinyl laurate, respectively. When the reactions were performed with capsaicin analogues of different acyl chain lengths, CALA exhibited a noticeable transesterification preference for medium-length capsaicin analogues. In an attempt to explore the catalytic limits of CALA, we performed the transesterification of capsaicin from Capsicum oleoresin. The results showed similar transesterification yields to those obtained with semi-pure capsaicin. Within our knowledge, this is the first report to achieve the synthesis of phenolic OH esters of capsaicin and capsaicin analogues by enzymatic means.

辣椒素类似物通常通过香草醛胺的酰胺基与脂肪酸衍生物的缩合来合成。选择进行该反应的酶是南极假丝酵母脂肪酶B；然而，该酶不能与香草基环的酚取代基反应。到目前为止，这只能通过化学方法实现，因此辣椒素酯的亲脂性和刺激性都比母体化合物高。为了寻找新的辣椒素衍生物，我们研究了南极假丝酵母对辣椒素和几种辣椒素类似物的酚羟基的酯交换作用脂肪酶A（CALA）与乙烯基酯。成功合成了辣椒素酯，与丁酸乙烯酯和月桂酸乙烯酯的反应产率分别为80.6％和57.5％。当用不同酰基链长度的辣椒素类似物进行反应时，CALA对中等长度的辣椒素类似物表现出明显的酯交换偏好。为了探索CALA的催化极限，我们进行了辣椒油树脂对辣椒素的酯交换反应。结果显示，酯交换率与半纯辣椒素相似。在我们的知识范围内，这是第一个通过酶促方法合成辣椒素和辣椒素类似物的酚羟基酯的报告。